KR20150016686A - Modified vinyl aromatic hydrocarbon-conjugated diene copolymer, method for preparing the same and asphalt composition comprising the same - Google Patents

Abstract

The present invention relates to a modified vinyl aromatic hydrocarbon-conjugated diene copolymer and an asphalt composition comprising the same capable of having uniform asphalt quality by minimizing phase separation on modified asphalt in manufacture during for the same amount of time by using a modified vinyl aromatic hydrocarbon-conjugated diene copolymer of chemical formula 1 as an asphalt modifying agent having compatibility with asphaltene having polarity among asphalt ingredients. The asphalt composition also can shorten manufacturing time required for having identical phase separation characteristics. In chemical formula 1, R^1, R^2 and R^3 are an alkylene group (-(CH_2)_n-, n=1-15), respectively; R^4, R^5, R^6, R^7 and R^9 are an alkyl group or an alkyl silyl group, respectively; R^8 is a C1-C15 alkyl group; P is a vinyl aromatic hydrocarbon-conjugated diene copolymer chain; a is an integer of 0-2; b is an integer of 0-2; and c is an integer of 1-3, wherein a+b+c=3.

Description

TECHNICAL FIELD The present invention relates to a modified vinyl aromatic hydrocarbon-conjugated diene copolymer, a modified vinyl aromatic hydrocarbon-conjugated diene copolymer, a process for producing the same, and an asphalt composition comprising the modified vinyl aromatic hydrocarbon-

The present invention relates to a modified vinyl aromatic hydrocarbon-conjugated diene copolymer and an asphalt composition containing the modified vinyl aromatic hydrocarbon-conjugated diene copolymer, and more particularly to a modified vinyl aromatic hydrocarbon-conjugated diene copolymer having an asphalt- The use of an aromatic hydrocarbon-conjugated diene copolymer enables the production of modified vinyl aromatic-conjugated dienes having a homogeneous asphalt quality by minimizing phase separation during the production of modified asphalt at the same time and shortening the production time required to have the same phase separation characteristics Copolymer, a process for producing the same, and an asphalt composition containing the same.

In Formula 1, R ^1, R ² and R ³ are each of 1 to 15 carbon atoms independently, an alkylene group _{(- (CH 2) n -} , n = 1 ~ 15) , ^{and, R 4, R 5, R} 6, R ⁷ and R ⁹ are each independently an alkyl group or an alkylsilyl group, R ⁸ is an alkyl group having 1 to 15 carbon atoms, and P is a vinyl aromatic hydrocarbon-conjugated diene copolymer chain.

In Formula 1, a is an integer of 0 to 2, b is an integer of 0 to 2, c is an integer of 1 to 3, and a + b + c satisfies 3.

Conventionally, asphalt used as road pavement and waterproofing material has been severely limited in its use due to problems such as low temperature cracking and high temperature plastic deformation.

Therefore, various reforming agents for asphalt have been actively studied and applied to improve the disadvantages of such asphalt.

As the asphalt modifier, a variety of high molecular materials such as an olefin / acrylic monomer copolymer, a vinyl aromatic hydrocarbon-conjugated diene random copolymer, and a vinyl aromatic hydrocarbon-conjugated diene block copolymer are used. Among them, a vinyl aromatic hydrocarbon-conjugated diene block copolymer It is most widely used because it has the effect of dramatically increasing the service temperature range and lifetime of asphalt by only a small amount of addition. However, since the dissolution rate of the asphalt modifier is low due to the incompatibility between the asphalt and the asphalt modifier, the modified asphalt preparation time is long, and when the asphalt modifier is partially dissolved, the phase separation progresses with time, A problem arises. The phenomenon of phase separation is a phenomenon in which an upper layer containing a large amount of a vinyl aromatic hydrocarbon-conjugated diene block copolymer and a lower layer containing a small amount are divided due to the incompatibility between the asphalt constituting the modified asphalt and the vinyl aromatic hydrocarbon-conjugated diene block copolymer . In other words, when the asphalt modifier is dissolved in the asphalt, the malt in the asphalt is absorbed by the asphalt modifier. As time passes, the asphalt modifier containing the maltine migrates to the upper layer, and the relatively high molecular weight, .

When the conventional asphalt modifier is applied to asphalt, problems of plastic deformation and low-temperature cracking can be solved. However, as the quality of the asphalt is lowered due to the continuous improvement of the refinery facilities, the asphalt component is increased and the asphalt and the existing asphalt modifier There is a problem in that the time for producing modified asphalt is prolonged.

Therefore, there is a need for a highly soluble asphalt modifier that can improve the phase separation of asphalt modifier and asphalt.

In order to solve the problems of the prior art as described above, the present invention provides an asphalt modifier having compatibility with asphaltenes having polarity among the asphalt components and capable of improving the phase separation phenomenon with asphalt, a process for producing the same, And the like.

Further, the present invention aims to provide an asphalt modifier which can shorten the production time required for the asphalt to have the same phase separation characteristics, a process for producing the same, and an asphalt composition containing the same.

These and other objects of the present invention can be achieved by the present invention described below.

In order to achieve the above object, the present invention provides a modified vinyl aromatic hydrocarbon-conjugated diene copolymer which is a polymer represented by the following general formula (1).

[Chemical Formula 1]

In Formula 1, R ^1, R ² and R ³ are each of 1 to 15 carbon atoms independently, an alkylene group _{(- (CH 2) n -} , n = 1 ~ 15) , ^{and, R 4, R 5, R} 6, R ⁷ and R ⁹ are each independently an alkyl group or an alkylsilyl group, R ⁸ is an alkyl group having 1 to 15 carbon atoms, and P is a vinyl aromatic hydrocarbon-conjugated diene copolymer chain.

In Formula 1, a is an integer of 0 to 2, b is an integer of 0 to 2, c is an integer of 1 to 3, and a + b + c satisfies 3.

And (a) polymerizing the conjugated diene monomer and the vinyl aromatic monomer with an organometallic compound in a solvent to form an active polymer having a metal terminal; And (b) introducing into the active polymer a compound represented by the following formula (2) to modify the vinyl aromatic hydrocarbon-conjugated diene copolymer.

In Formula ₂ R _1, R 2 and R ₃ are each independently an alkylene group _{(- (CH 2) n -} , n = 1 ~ 15) , _{and, R 4, R 5, R} 6, R 7 and R ₉ is R ₈ is an alkyl group having 1 to 15 carbon atoms, and m is an integer of 0 to 2.

The present disclosure also relates to a thermoplastic resin composition comprising i) a modified vinyl aromatic hydrocarbon-conjugated diene copolymer as described above as an asphalt modifier; And ii) an asphalt; and the like.

As described above, according to the present invention, it is possible to provide a modified vinyl aromatic hydrocarbon-based resin composition capable of having uniform asphalt quality by minimizing phase separation at the time of manufacturing the modified asphalt and shortening the manufacturing time required to have the same phase- A conjugated diene copolymer, a process for producing the same, an asphalt composition containing the same and a modified asphalt.

1 is a photograph of a process of melting an asphalt modifier in an asphalt composition using a fluorescence microscope. (A) is a photograph at a magnification of 400 before the modifier is melted, (B) is a photograph at a magnification of 400 at the time of melting the modifier for 2 hours, and (C) is a photograph at a magnification of 400 at the time of complete melting of the modifier.

Hereinafter, the modified vinyl aromatic hydrocarbon-conjugated diene copolymer of the present invention, a process for producing the modified vinyl aromatic hydrocarbon-conjugated diene copolymer, an asphalt composition containing the modified vinyl aromatic hydrocarbon-conjugated diene copolymer as a modifier, and the modified asphalt produced from the asphalt composition will be described in detail .

denaturalization Vinyl aromatic  hydrocarbon- Conjugated diene  Copolymer

The modified vinyl aromatic hydrocarbon-conjugated diene copolymer of the present invention is a modified vinyl aromatic hydrocarbon-conjugated diene copolymer represented by the following formula (1).

[Chemical Formula 1]

In Formula 1, R _1, R ₂ and R ₃ are each of 1 to 15 carbon atoms independently, an alkylene group _{(- (CH 2) n -} , n = 1 ~ 15) , _{and, R 4, R 5, R} 6, R ₇ and R ₉ are independently an alkyl group or an alkylsilyl group, R ₈ is an alkyl group having 1 to 15 carbon atoms, and P is a vinyl aromatic hydrocarbon-conjugated diene-based copolymer chain.

In formula (1), a is 0, 1 or 2, b is 0, 1 or 2, c is 1, 2 or 3, and a + b + c satisfies 3.

R ₁ , R ₂ and R ₃ are, for example, an alkylene group, an alkylene group having 1 to 15 carbon atoms or an alkylene group having 1 to 8 carbon atoms.

In another example, R ₁ , R _2, and R ₃ are bivalent alkylsilyl groups, bivalent alkylsilyl groups having 1 to 15 carbon atoms, or alkylsilyl groups having 1 to 8 carbon atoms.

The alkylsilyl group of the present disclosure can be, for example, an alkylene-silyl-alkylene, silyl-alkylene or alkylene-silyl linked group.

R ₄ , R ₅ , R ₆ , R ₇ And R ₉ is, for example, an alkyl group or an alkyl group having 1 to 15 carbon atoms.

The vinyl aromatic hydrocarbon-conjugated diene copolymer chain may be, for example, a chain comprising a conjugated diene monomer and a vinyl aromatic monomer.

As another example, the vinyl aromatic hydrocarbon-conjugated diene copolymer chain may contain 1 to 50% by weight, 10 to 40% by weight or 20 to 20% by weight, based on 100% by weight of the total of the conjugated diene monomer and the vinyl aromatic monomer, 35% by weight of the copolymer chain.

The copolymer chain comprising the conjugated dienic monomer and the vinyl aromatic monomer may be, for example, a random or block copolymer chain.

Examples of the conjugated diene monomer include 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, Butadiene, and another example may be 1,3-butadiene, but the present invention is not limited thereto.

Examples of the vinyl aromatic monomer include styrene,? -Methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- (p- -Vinyl-5-hexynaphthalene, and still another example may be styrene or? -Methylstyrene, but is not limited thereto.

The number average molecular weight of the modified vinyl aromatic hydrocarbon-conjugated diene copolymer may be, for example, 50,000 to 500,000 g / mol, 50,000 to 350,000 g / mol, or 80,000 to 350,000 g / mol.

The modified vinyl aromatic hydrocarbon-conjugated diene copolymer may have a vinyl content of 5 to 60%, 10 to 40%, or 10 to 30%, for example.

Here, the vinyl content means the content of the vinyl group-containing monomer or the content of the 1,2-added conjugated diene monomer, not 1,4-addition to 100% by weight of the conjugated diene-based monomer.

Further, the present invention relates to a method for producing a polymer electrolyte membrane, comprising: (a) polymerizing a conjugated diene monomer and a vinyl aromatic monomer using an organometallic compound in a solvent to form an active polymer having a metal terminal; And (b) introducing into the active polymer a compound represented by the following formula (2) to modify the vinyl aromatic hydrocarbon-conjugated diene copolymer.

(2)

In Formula ₂ R _1, R 2 and R ₃ are each independently an alkylene group _{(- (CH 2) n -} , n = 1 ~ 15) , _{and, R 4, R 5, R} 6, R 7 and R ₉ is R ₈ is an alkyl group having 1 to 15 carbon atoms, and m is 0, 1 or 2.

R ₁ to R ₉ are the same as described above.

The vinyl aromatic hydrocarbon-conjugated diene copolymer before the modification of the modified vinyl aromatic hydrocarbon-conjugated diene copolymer is obtained by copolymerizing the vinyl aromatic monomer and the conjugated diene monomer.

In the polymerization process of the vinyl aromatic hydrocarbon-conjugated diene copolymer, polymerization can be carried out by supplying a polymerization initiator to a reactor for copolymerizing the conjugated dienic monomer and the vinyl aromatic monomer.

In the step (a), for example, the vinyl aromatic monomer may be firstly polymerized, and then the conjugated diene monomer may be added to polymerize. In this case, a block copolymer may be prepared.

As another example, in the step (a), the conjugated diene monomer may first be polymerized, and then the vinyl aromatic monomer may be added to polymerize.

As another example, in the step (a), the conjugated diene-based monomer and the vinyl aromatic monomer may be mixed and polymerized to initiate polymerization. In this case, a random copolymer may be produced.

Examples of the conjugated diene monomer include 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, Butadiene, and another example may be 1,3-butadiene, but the present invention is not limited thereto.

Examples of the vinyl aromatic monomer include styrene,? -Methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- (p- -Vinyl-5-hexynaphthalene, and still another example may be styrene or? -Methylstyrene, but is not limited thereto.

The vinyl aromatic monomer may be 1-50 wt%, 10-40 wt% or 20-35 wt% based on 100 wt% of the total of the conjugated diene monomer and the vinyl aromatic monomer.

The solvent may be at least one selected from the group consisting of hydrocarbons or n-pentane, n-hexane, n-heptane, isooctane, cyclohexane, toluene, benzene and xylene.

The organic metal compound may be at least one selected from the group consisting of an organic alkali metal compound, an organic lithium compound, an organic sodium compound, an organic potassium compound, an organic rubidium compound and an organic cesium compound.

As another example, the organometallic compound may be at least one selected from the group consisting of methyllithium, ethyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, Naphthyl lithium, n-eicosyllithium, 4-butylphenyllithium, 4-tolylithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium and 4-cyclopentyllithium Or more.

 In another example, the organometallic compound is n-butyllithium, sec-butyllithium, or a mixture thereof.

In another example, the organometallic compound is selected from the group consisting of naphthyl sodium, naphthyl potassium, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide and potassium amide And may be used in combination with other organometallic compounds.

The organometallic compound is used in an amount of 0.01 to 10 mmol, 0.05 to 7 mmol, or 0.1 to 5 mmol based on 100 g of the total amount of the monomers.

The molar ratio of the organometallic compound to the compound represented by Formula 2 is, for example, 1: 0.1 to 1:10, or 1: 0.5 to 1: 2.

The active polymer having the metal terminal of the present invention means a polymer to which a polymer anion and a metal cation are bonded.

The method for producing the modified vinyl aromatic hydrocarbon-conjugated diene copolymer of the present invention can be polymerized by further adding a polar additive in the polymerization of (a).

The polar additive may be, for example, a base, and in another example, an ether, an amine, or a mixture thereof, or a mixed solvent of tetrahydrofuran, ditetrahydrofuryl propane, diethyl ether, cyclo- (Dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine, and tetramethylethylenediamine Ethylenediamine, and another example is diethtrahydropropyl propane, triethylamine or tetramethylethylenediamine.

The polymerization of (a) may be anionic polymerization, for example.

As another example, the polymerization of (a) may be a living anionic polymerization in which an active terminal is obtained by a growth reaction with an anion.

The polymerization temperature of (a) is, for example, -20 to 200 占 폚, 0 占 폚 to 150 占 폚, or 10 to 120 占 폚.

As the step (b), for example, one or more, or two or three compounds represented by the formula (2) may be added.

The (b) denaturation step is carried out, for example, at 0 to 150 ° C or 80 to 130 ° C for 1 minute to 5 hours.

The modified vinyl aromatic hydrocarbon-conjugated diene copolymer of the present invention is characterized in that it is produced, for example, according to the above-described method for producing a modified vinyl aromatic-hydrocarbon-conjugated diene copolymer.

asphalt Modifier

The asphalt modifier of the present invention may, for example, comprise 10 to 100% by weight of the modified vinyl aromatic-hydrocarbon-conjugated diene copolymer and 0 to 90% by weight of the other conjugated diene-based polymer.

As another example, the asphalt modifier of the present invention may comprise 20 to 99% by weight of the modified vinyl aromatic hydrocarbon-conjugated diene copolymer and 1 to 80% by weight of the other conjugated diene-based polymer.

The conjugated diene polymer is not particularly limited as long as it can be used as an asphalt modifier. For example, a vinyl aromatic hydrocarbon and a conjugated diene are sequentially added to a reactor containing a hydrocarbon solvent and an organolithium compound, Deg.] C and a pressure range (0.1 to 10 bar) in which the reactant can be maintained in a liquid phase, the polymerization is continued until the consumption rate of the monomer is 99% or more, and then the activity of the active polymer is removed by the addition of water or alcohol, Or by further adding a coupling agent thereafter, connecting the conjugated diene blocks between the prepared block copolymers, and then removing the activity of the active polymer by adding water or an alcohol and terminating the polymerization.

Examples of the conjugated diene polymer include styrene-butadiene rubber (SBR), styrene-isoprene-styrene (SIS) block copolymer, styrene-ethylene-butylene-styrene (SEBS), polybutadiene, natural rubber, have.

The hydrocarbon solvent may be at least one member selected from the group consisting of n-pentane, n-hexane, n-heptane, isooctane, cyclohexane, toluene, benzene, xylene and naphthalene- Cyclohexane or a mixture thereof.

The polar solvent may be added to the hydrocarbon solvent, which serves to control the content of the vinyl structure and to improve the polymerization rate during the polymerization of the conjugated diene.

The polar solvent may be at least one selected from the group consisting of tetrahydrofuran, ethyl ether, tetramethylethylenediamine and benzofuran, and more preferably tetrahydrofuran.

The free lithium compound is preferably an alkyl lithium compound, more preferably an alkyl lithium compound having an alkyl group having 3 to 10 carbon atoms.

The organic lithium compound may be, for example, methyl lithium, ethyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium or tert-butyl lithium,

Asphalt composition

The asphalt composition of the present invention is characterized by containing the asphalt modifier and the asphalt.

The asphalt can be a residue obtained when refining crude oil, and is mainly composed of hydrogen and carbon, and can be made of hydrocarbon compounds having a small amount of nitrogen, sulfur, or oxygen bonded thereto.

As the asphalt, straight asphalt, cut-back asphalt, goose asphalt, blown asphalt, emulsified asphalt or sebum (PG) grade asphalt may be used.

Among them, the straight asphalt can be used as a raw material for various petroleum-based asphalt containing a large amount of bituminous material which is not decomposed as a final residue obtained by distillation of the crude oil at the atmospheric distillation column and distillation of the residual atmospheric residue. Commercialized straight asphalt includes AP-3 or AP-5 supplied by SK Energy or GS Caltex.

The asphalt may comprise asphaltenes.

The asphalt may contain 1 to 40% by weight or 5 to 30% by weight of asphaltenes, for example.

The weight mixing ratio of the asphalt modifier and the asphalt is, for example, 0.1: 99.9 to 20: 80, or 1:99 to 10:90. In this case, physical properties of the asphalt composition for plastic deformation and fatigue cracks are improved.

The modified asphalt of the present invention is characterized in that it is produced from the asphalt composition.

The softening point herein refers to the high temperature properties of the modified asphalt according to the American Society for Testing and Materials (ASTM) D36, which upon heating of water or glycerin at 5 [deg.] C per minute begins to soften the specimen It can be defined as the temperature when a ball of 9.525 mm in diameter and 3.5 g in weight located on the specimen is struck by 1 inch.

The elongation (5 캜) of the present invention represents the low-temperature properties of modified asphalt according to ASTM D113. When the specimen is pulled in both directions in a thermostatic chamber maintained at 5 캜, the elongation is increased to just before the specimen is broken Can be defined.

The storage stability of the present invention was measured by measuring the amount of modified asphalt in an aluminum tube, leaving it in an oven at 163 캜 for 48 hours, cooling it in a cooler at -5 캜, The upper and lower softening points are measured by the ASTM D36 method. At this time, phase separation does not occur when the temperature difference between the upper and lower layers is within 2 ° C. Storage stability is better as the difference is smaller. When the solubility or compatibility of the asphalt modifier is excellent, the storage time is short and the storage stability is good.

The modified asphalt may be, for example, modified asphalt for road pavement.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.

[Example]

Example  One

≪ Preparation of Modified Styrene-Butadiene Block Copolymer >

1470 g of purified cyclohexane and 93 g of styrene were charged into a 3 L reactor purged with nitrogen, and the temperature was raised to 70 캜 while stirring. The styrene block was polymerized by adding 0.36 g of n-butyllithium to the mixed solution of cyclohexane and styrene at 70 DEG C, 207 g of butadiene was added thereto, and polymerization was continued until the butadiene completely consumed. After the butadiene is completely consumed, 0.69 g of 3-dimethylamino-2- (dimethylaminomethyl) propyltrimethoxysilane represented by the following formula 3 is added. After completion of the reaction, 0.1 g of water was added to the reactor to remove the activity of the active polymer. Then, 1.74 g of an antioxidant Irganox 1076 (BASF) and 0.9 g of TNPP (Weston Chemical Co.) To prepare a modified styrene-butadiene block copolymer solution having a number average molecular weight of 112,000 g / mol.

≪ Preparation of crumb by polymer recovery from polymer solution >

In order to recover only the polymer from the polymer solution, a stripping process is generally performed. Namely, 2.5 g of Tamol (TAMOL) and 0.5 g of CaCl ₂ were added to 3 L of water and boiled. Subsequently, when the polymer solution is slowly dropped into boiling water, the solvent in the solution is evaporated, and the polymer is agglomerated in water and dispersed in water to a size of 1 to 20 mm. The polymer produced in the above process was recovered and dried in an oven at 60 ° C. for 16 hours to obtain a crumb-shaped polymer.

≪ Preparation of asphalt composition and modified asphalt &

AP-5 product having physical properties as shown in Table 1 purchased from SK Innovation Co., Ltd. was used as the asphalt.

Intrusion (dmm) Softening point (℃) Viscosity (cPs) 100 ℃ 120 DEG C 135 ℃ SK AP-5 60 46.4 to 47.7 3850-3900 1000 ~ 1030 440 to 460

In Table 1, penetration was measured at 25 DEG C according to ASTM D946, the softening point was measured according to ASTM D36, and the viscosity was measured according to ASTM D4402 under the condition of spindle 27 using Brookfield DV-II + Pro Model.

500 g of the AP-5 was placed in a mixing container, and 23.37 g of the polymer crumb was charged at 160 ° C and a stirring speed of 2,000 rpm. The temperature was 180 ° C and the stirring speed was 2,500 rpm And the mixture was stirred for 50 minutes. Then, 0.524 g of sulfur was added and stirred for 10 minutes. The stirring speed was lowered to 300 rpm and stirred for 60 minutes to prepare modified asphalt. The total production time of the dissolved modified asphalt was 2 hours and sampled for physical property measurement.

Comparative Example  One

Styrene and n-butyllithium were introduced at a temperature of 60 ° C. and 0.31 g of n-butyllithium was added thereto to prepare a modified styrene-butadiene block copolymer of the formula 3, Except that 0.35 g of dicumylmethylsilane was used instead of dimethylamino-2- (dimethylaminomethyl) propyltrimethoxysilane, the unmodified styrene-butadiene copolymer having a number average molecular weight of 111,000 g / mol was obtained in the same manner as in Example 1, Butadiene block copolymer solution was prepared. A polymer crumb, an asphalt composition and a modified asphalt were prepared in the same manner as in Example 1. The total production time of the dissolved modified asphalt was 2 hours and sampled for physical property measurement.

Example  2

In the < Preparation of Asphalt Composition and Modified Asphalt > in Example 1, the stirring speed was reduced to 300 rpm and the stirring speed was lowered to 300 rpm instead of stirring for 60 minutes, followed by stirring until the polymer crumb completely dissolved by a fluorescence microscope A modified styrene-butadiene block copolymer solution, a polymer crumb, an asphalt composition and a modified asphalt were prepared in the same manner as in Example 1. The total production time of the dissolved modified asphalt was 2 hours and 50 minutes, and the samples were sampled for property measurement.

Comparative Example 2

In the <Preparation of Asphalt Composition and Modified Asphalt> of Comparative Example 1, the stirring speed was reduced to 300 rpm and the stirring speed was lowered to 300 rpm instead of stirring for 60 minutes, followed by stirring until the polymer crumb was completely dissolved by a fluorescence microscope An unmodified styrene-butadiene block copolymer solution, a polymer crumb, an asphalt composition and a modified asphalt were prepared in the same manner as in Comparative Example 1, The total production time of the dissolved modified asphalt was 3 hours and 30 minutes, and the samples were sampled for physical property measurement.

 [Test Example]

Properties of the modified asphalt prepared in Examples 1 to 2 and Comparative Examples 1 and 2 were measured by the following methods, and the results are shown in Table 2 below.

Number Average Molecular Weight: Each sample was dissolved in tetrahydrofuran (THF) for 30 minutes and then loaded on GPC (Gel Permeation Chromatography, manufactured by Waters) and flowed. Then, the standard of PS (Polystyrene) The molecular weight was measured in comparison with the molecular weight.

* Softening point: measured according to ASTM D36.

* Shindo (5 ° C): The specimen was left in a constant temperature water bath at 5 ° C for 1 hour and measured according to ASTM D113.

Viscosity (135 占 폚): Measured according to ASTM D4402 under the condition of spindle 27 using Brookfield DV-II + Pro Model.

      * Storage stability: 50 g of modified asphalt was weighed in an aluminum tube, allowed to stand in an oven at 163 ° C for 48 hours, allowed to stand in a cooler at -5 ° C for 4 hours or more, and then the upper and lower softening points were measured by ASTM D36 . When the temperature difference is within 2 ℃, phase separation does not occur. The smaller the difference, the better the storage stability.

division Total manufacturing time Softening point Shindo (5 ℃) Viscosity (135 ° C) Storage stability (° C) (mm) (cPs) (° C) Example 1 2 hours 86.1 207 1625 16.7 Example 2 2 hours 50 minutes 74.5 220 1700 0.1 Comparative Example 1 2 hours 90.1 218 1920 20.7 Comparative Example 2 3 hours and 30 minutes 82.9 208 2055 0

Example 1 of the present invention corresponds to Comparative Example 1 as a modified asphalt containing a modified vinyl aromatic hydrocarbon-conjugated diene-based copolymer, and Example 2 corresponds to Comparative Example 2.

As shown in Table 2, when the total production time of the modified asphalt was 2 hours, it was confirmed that the storage stability of Example 1 and Comparative Example 1 were not completely dissolved at 16.7 ° C and 20.7 ° C, respectively. In particular, it was found that the solubility of the modified vinyl aromatic-hydrocarbon-conjugated diene copolymer of Example 1 was better than that of Comparative Example 1, which was worse than that of Example 1 by about 4 ° C.

Based on the results of Example 1 and Comparative Example 1, the total production time of the modified asphalt was increased. As shown in FIG. 1, the particles of the modified or unmodified styrene-butadiene block copolymer were completely After dissolution, the physical properties were compared.

As shown in Table 2, when the results of Example 2 and Comparative Example 2 were compared, it was found that the storage stability of Example 2 took a total of 2 hours and 50 minutes to reach a completely dissolved state of 2 ° C or less, 2, it took 3 hours and 30 minutes in total, and it was confirmed that Example 2 was shorter than Comparative Example 2 by about 40 minutes. That is, it was confirmed that the solubility of the modified vinyl aromatic hydrocarbon-conjugated diene copolymer of Example 2 was superior to that of the unmodified vinyl aromatic hydrocarbon-conjugated diene copolymer of Comparative Example 2. In addition, the viscosity of Example 2 was lower than that of Comparative Example 2, indicating that the workability was somewhat superior.

The modified vinyl aromatic hydrocarbon-conjugated diene copolymer contains a large amount of dimethylamino groups in the vinyl aromatic hydrocarbon-conjugated diene chain, so that the affinity of the modified vinyl aromatic hydrocarbon-conjugated diene copolymer with the asphaltene of polarity can be increased, It was confirmed that the effect of shortening the manufacturing time of the modified asphalt was confirmed by increasing the compatibility and dispersibility.

In addition to modifying the vinyl aromatic hydrocarbon-conjugated diene copolymer, the basic structure that affects the modified asphalt properties such as the molecular weight of the vinyl aromatic hydrocarbon-conjugated diene copolymer itself or the monomer-to-monomer content ratio is not changed, .

Claims (17)

Is a polymer represented by the following formula (1)
Modified vinyl aromatic hydrocarbon-conjugated diene copolymer.
[Chemical Formula 1]

Wherein R ¹ , R ² and R ³ are each independently an alkylene group having 1 to 15 carbon atoms, and R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁹ are each independently an alkyl group or an alkylsilyl group, R ⁸ is an alkyl group having 1 to 15 carbon atoms, and P is a vinyl aromatic hydrocarbon-conjugated diene copolymer chain.
In Formula 1, a is 0, 1 or 2, b is 0, 1 or 2, c is 1, 2 or 3, and a + b + c satisfies 3. The method according to claim 1,
Wherein the vinyl aromatic hydrocarbon-conjugated diene copolymer chain is a random or block copolymer chain comprising a conjugated diene monomer and a vinyl aromatic monomer
Modified vinyl aromatic hydrocarbon-conjugated diene copolymer. The method according to claim 1,
Wherein the modified vinyl aromatic-hydrocarbon-conjugated diene copolymer has a number average molecular weight of 50,000 to 500,000 g / mol
Modified vinyl aromatic hydrocarbon-conjugated diene copolymer. The method according to claim 1,
The modified vinyl aromatic-hydrocarbon-conjugated diene copolymer is characterized by having a vinyl content of 5 to 60%
Modified vinyl aromatic hydrocarbon-conjugated diene copolymer. The method according to claim 1,
Wherein the vinyl aromatic hydrocarbon-conjugated diene copolymer chain comprises 1 to 50 wt% of a vinyl aromatic monomer based on 100 wt% of the total of the conjugated diene monomer and the vinyl aromatic monomer
Modified vinyl aromatic hydrocarbon-conjugated diene copolymer. (a) polymerizing a conjugated diene monomer and a vinyl aromatic monomer with an organometallic compound in a solvent to form an active polymer having a metal terminal; And
(b) introducing into the active polymer a compound represented by the following formula (2)
Modified vinyl aromatic hydrocarbon-conjugated diene copolymer.
(2)

The method according to claim 6,
The organometallic compound is used in an amount of 0.01 to 10 mmol based on 100 g of the total amount of the monomers.
Modified vinyl aromatic hydrocarbon-conjugated diene copolymer. The method according to claim 6,
Wherein the molar ratio of the organometallic compound to the compound represented by the formula (2) is 1: 0.1 to 1:10
Modified vinyl aromatic hydrocarbon-conjugated diene copolymer. A modified vinyl aromatic hydrocarbon-conjugated diene copolymer produced by the process for producing the modified vinyl aromatic hydrocarbon-conjugated diene copolymer of any one of claims 6 to 8. A modified vinyl aromatic hydrocarbon-conjugated diene copolymer according to any one of claims 1 to 5
Asphalt modifier. 11. The method of claim 10,
Wherein the asphalt modifier comprises 10 to 100% by weight of the modified vinyl aromatic-hydrocarbon-conjugated diene copolymer and 0 to 90% by weight of the other conjugated diene-based polymer
Asphalt modifier. 12. The method of claim 11,
Wherein the conjugated diene polymer is at least one selected from the group consisting of a vinyl aromatic hydrocarbon-conjugated diene copolymer, a butadiene rubber, and a natural rubber
Asphalt modifier. An asphalt modifier of claim 10; And asphalt;
Asphalt composition. 14. The method of claim 13,
Characterized in that the asphalt comprises asphaltenes
Asphalt composition. 14. The method of claim 13,
The asphalt composition is characterized in that the weight mixing ratio of the asphalt modifier to the asphalt is 0.1: 99.9 to 20:80
Asphalt composition. A modified asphalt prepared from the asphalt composition of claim 13. 17. The method of claim 16,
Characterized in that the modified asphalt is an asphalt for road pavement
Modified asphalt.

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